CN102066539B - Castor oil fatty acid based estolide esters and their derivatives as potential lubricant base stocks - Google Patents

Castor oil fatty acid based estolide esters and their derivatives as potential lubricant base stocks Download PDF

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CN102066539B
CN102066539B CN200980123247.XA CN200980123247A CN102066539B CN 102066539 B CN102066539 B CN 102066539B CN 200980123247 A CN200980123247 A CN 200980123247A CN 102066539 B CN102066539 B CN 102066539B
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long
ester
chain ester
acid
castor oil
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CN102066539A (en
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萨蒂亚·巴斯卡·波图拉
温卡塔·帕德马贾·科佩斯瓦拉
温卡塔·苏里亚·科佩斯瓦拉·拉奥·巴姆蒂帕梯
沙拉瓦南·克里希纳库马尔
巴德里·纳拉亚纳·普拉萨德·拉沙普迪
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Council of Scientific and Industrial Research CSIR
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/40—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C10M2207/2895—Partial esters containing free hydroxy groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/081—Biodegradable compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Castor oil was hydrolysed to castor fatty acids and self condensed to get a ricinoleic acid- based estolide of about 95 acid value. The carboxylic group of the estolide on subsequent esterification with linear or branched chain alcohols and also on acetylation of free hydroxy group yielded castor oil fatty acids based estolide esters and their acetates. All the products were evaluated for total acid number (TAN), viscosity, viscosity index, pour point, flash point, and copper strip corrosion and found to be potential lubricant basestocks.

Description

Castor Oil Fatty Acid base long-chain ester ester is with them as potential lube oil base stocks Derivative
Invention field
The present invention relates to Castor Oil Fatty Acid-straight chain of base long-chain ester (estolides) and the preparation of isoalkyl ester and They are as the derivative of potential lube oil base stocks.
Background of invention
Vegetable oil is considered as preparing the potential candidate of biological lubricant oil base stock to replace the mineral of routine Oil-base lubricating oil and synthetic ester.Plant oil lubricant is due to their enhanced biological degradabilities, lower toxicity and some its Its property but the attractive alternatives of mineral oil-based lubricating oil.
Long-chain ester is the ester based on vegetable oil for the class, and it is in a kind of carboxylic acid functional of aliphatic acid in another kind of aliphatic acid Unsaturated double-bond position reaction is formed during ester bond with being formed, and this product is known as long-chain ester.The secondary key of long-chain ester (secondary linkage) than triglycerides more resistant to hydrolysis, and the unique texture of long-chain ester obtain for some apply, thing Rationality matter is much better than the material [Inform, page 15,515 (2004)] of the physical property of vegetable oil and mineral oil.
Be characterized by excellent properties as lube oil base stocks derived from oleic acid and C6 to C14 saturated fat The ester of the long-chain ester of acid has been described in Industrial Crops and Products (2001), and 13 (1), in 11-20. In another research, the oleic acid long-chain ester of saturate end-blocking is esterified by 2-Ethylhexyl Alcohol, obtains corresponding ester [Industrial Crops and Products, page 18,183 (2003)；United States Patent (USP) US 6,018,063 (2002) and US 6,316,649 (2001)].These cocounut oil-oleic acid long-chain ester ester show excellent cryogenic property (- 36 DEG C) and with current plant oil-base Commercial materials are compared, the oil base stock as biodegradable lube oil and functional fluid preferably.
In described another type of long-chain ester, the hydroxy fatty acid of castor oil can easily be changed into by homopolymerization Long-chain ester [J.Am.Oil Chem.Soc.42；Page 428 (1965).Connect different from the carboxylic acid functional when a kind of aliphatic acid The normal long-chain ester being formed with forming oligoester to the unsaturated position of another kind of aliphatic acid, the aliphatic acid of castor-oil plant has offer ester Change and position occurs to prepare the hydroxy functional group of long-chain ester.
Castor oil is the attractive raw material of industry of several functional compounds for preparation including lubricating oil [J.Am.Oil Chem.Soc.51, page 65 (1974), J.Am.Oil Chem.Soc.48, page 758 (1971)].Up to The presence of the castor oil acid (hydroxy fatty acid (12- hydroxyl 9 cis-octadecenoic acid)) of 85-90% makes castor oil as there being suction The lube oil base stocks of gravitation show especially.
The secondary alcohol ester of carboxylic acid, the ricinoleate ester of such as secondary alcohol is by making the ester of carboxylic acid and secondary alcohol in organic metal ester In the presence of exchange catalysts, preparation, is reported in United States Patent (USP) US 6,407,272 (2002), they can serve as lubricant.
Leix gram is lazy to strangle the long-chain ester of (Lesquerella) and castor-oil plant triglycerides and oleic acid it has been reported that in Journal Of the American Oil Chemists ' Society, in page 79,1227 (2002).Leix gram is lazy to strangle and castor-oil plant hydroxyl The synthesis of triglycerides and physical property are reported in Industrial Crops and Products, page 23,256 (2006) In.Leix gram is lazy strangle and castor oil pass through in the presence of 2 ethyl hexanoic acid tin catalyst (0.1 weight %) with saturated fatty acid (C2-C18) react and utilize the condensation of hydroxyl and corresponding acid anhydrides or heat in 200 DEG C under vacuo, and it is corresponding to change into them Long-chain ester.
Leix gram is lazy to strangle the long-chain ester with several different types of saturations, unsaturation and branched chain fatty acid with castor fatty acid It has been reported that in Industrial Corps and Products, page 23,54 (2006).The lazy Le of castor-oil plant and Leix gram is grown Chain ester ester has optimal cold temperature (cold temperature) property when with oleic acid or Branched fatty acid blocked.With long-chain Saturation in ester increases, and pour point and cloud point also increase.
Goal of the invention
Present invention is primarily targeted at preparing Castor Oil Fatty Acid-base long-chain ester and their acetic acid esters.
Further object is that preparing linear ester and the isoalkyl ester of above-mentioned long-chain ester.
Another object of the present invention is for the Arrcostab of long-chain ester and isoalkyl ester to change into their acetic acid esters, with Reduce viscosity in the case of there is no impact pour point and flash-point.
A further object of the present invention be by1H NMR determines both ester moiety and acetate moieties rough Formation in long-chain ester.
The physicochemical properties providing these esters are also one object of the present invention.
It is yet a further object of the present invention to provide family's long-chain ester, described long-chain ester is biodegradable and has Oxidation stability, low temperature and the viscometric properties needing.
Other objects and advantages of the present invention will become clear from from the following description.
Summary of the invention
In the present invention it was recently reported that the new long-chain of family derived from the Castor Oil Fatty Acid long-chain ester with about 95 acid numbers Ester compounds.Used in the present invention, Castor Oil Fatty Acid contains the castor oil acid being not less than 84%.
Detailed Description Of The Invention
Therefore, the present invention provides a kind of long-chain ester compounds of formula 1：
Formula 1
Wherein the value of n is 1, and wherein the mean value of n makes the acid number of long-chain ester be equal to 95 equal to 1, and it corresponds to described The castor oil acid of average two molecules in long-chain ester, R1 is side chain or the straight-chain hydrocarbons of C1 to C8；R2Part is selected from hydrogen, CH3CO group The group becoming.
In one embodiment of the invention, wherein R1Part is selected from methyl, isopropyl, butyl, hexyl, 2- ethyl The group of hexyl composition, and R2Part is selected from hydrogen, CH3The group of CO composition.
Therefore the present invention also provides a kind of method of the long-chain ester for preparing formula 1 according to claim 1, its Described in method include：
I () saponification castor oil obtains described castor oil acid, by described castor oil acid between 175 to 190 DEG C in the range of Temperature, heat time in the range of between 3 to 5hr under an inert atmosphere, obtain the long-chain ester compounds of formula 1, wherein n's is flat Average is 1, and R1 and R2 is H,
(ii) selected from sulfuric acid or SnCl2In catalyst in the presence of, reflux temperature or between 140 to 160 DEG C model Temperature in enclosing, makes the alcohol of the long-chain ester compounds 1 and carbon C1-C8 obtaining in step (i) such as methyl alcohol, isopropanol, butanol, just Hexanol, 2-Ethylhexyl Alcohol react the time in the range of between 3 to 8hr, to obtain corresponding long-chain ester ester,
(iii) the long-chain ester ester obtaining in step (ii) is made to react with acetic anhydride and pyridine, to obtain the long-chain of formula 1 The acetyl compounds of ester ester, wherein R1Partly selected from methyl, isopropyl, butyl, hexyl, the group of 2- ethylhexyl composition, And R2Part is CH3CO.
In one embodiment of the invention, the acid number of wherein said compound is 0.5mgKOH/g.
In another embodiment of the present invention, the compound of its Chinese style 1 be suitable for former state or with blend composition or interpolation Agent is together as the oil base stock of functional fluid.
The vegetable oil based lubricating oil of the present invention is prepared by triglycerides, and described triglycerides is by having a hydroxyl and one The aliphatic acid of unsaturated position is constituted as the saturation of main component and non-hydroxyl and unrighted acid, and most preferably comes Source is castor oil.
Castor oil contains the castor oil acid (12- hydroxyl -9- cis-octadecenoic acid) of about 85-90%, by saponification route And change into its aliphatic acid.Make the Castor Oil Fatty Acid (AV 195) obtaining in high temperature, be all polymerized to about 95 acid numbers under reduced pressure Castor oil acid-base long-chain ester.In this step process, acid number is reduced to 95 from 195, thus showing the formation of long-chain ester.
In the next step, long-chain ester changes into linear ester using straight chain alcohol and isoalkyl alcohol in the presence of a catalyst With isoalkyl ester.Finally, these esters by using the acetylizing agent that is made up of the mixture of acetic anhydride and pyridine and acetylation.
The product being formed has structures below, wherein R1It is alkyl chain, and R2It is H or acetyl group：
Wherein mean value=1 of n (acid numbers corresponding to 95).
In product ester and the formation both acetate moieties all by1H NMR spectra is determined.All products1H NMR spectra is determined clearly the formation in accordingly rough long-chain ester of Arrcostab and acetate groups.
Evaluate the total acid number (TAN) of all products, viscosity, viscosity index (VI), pour point, flash-point and copper strip corrosion and it was found that They are potential lube oil base stocks.
It is an advantage of the current invention that：These products are by the such as castor oil synthesis of unedible renewable resource.Synthesis Product show high viscosity index (VI), high flash-point and low pour point characteristic.
The present invention is further by following reality that is being given merely for example purpose and being not intended to the restriction scope of the invention Apply example to be described.Although the present invention is described already in connection with embodiment and with reference to its embodiment, but it is clear that mirror In foregoing description, many alternative improvement and variant are clearly for a person skilled in the art, therefore in the present invention It is intended to including these and all of alternative that can fall within the scope and spirit of the invention, variant and improvement.
Embodiment 1
The preparation of the long-chain ester of Castor Oil Fatty Acid：Castor oil (1000g) is put in three neck round bottom, and heats To 80 DEG C.Under agitation sodium hydroxide solution (145g, NaOH/1200ml, water) is slowly added to wherein.To stir Continue 3 hours at 85 DEG C.After completion of saponification, the diluted hydrochloric acid aqueous solution (6N) of q.s is added in reactant mixture, with Reduce fat completely sour soap in the pH less than 4.Stirring is continued 15 minutes.Reactant mixture is cooled to room temperature and uses ether Extraction.Ether layer is washed with water to remove hydrochloric acid.Organic layer is made to pass through sodium sulphate, to remove the water of suspension.By ether true Empty lower removing, obtains Castor Oil Fatty Acid with the yield of 920g.In the case of under agitation, under a nitrogen, by castor oil acid (800g) it is heated to 185 DEG C.Sample is extracted on synchronism ground out, to monitor acid number, so that it is determined that the degree that long-chain ester is formed.Realizing After 95 required acid number, terminating reaction, wherein 95 required acid number is the long-chain ester of the castor oil acid with two units Theoretical acid number.The yield of product is 720g.
Embodiment 2
The preparation of long-chain ester methyl ester：By acid number be 95 Castor Oil Fatty Acid long-chain ester (400g) with containing 2% sulfuric acid Methyl alcohol (4000ml) flows back together.Process by thin-layer chromatography monitoring esterification.After completion of the reaction, content is cooled down, use second Acetoacetic ester extracts and washes with water.Make organic layer pass through sodium sulphate, and distill excessive alcohol and ethyl acetate under reduced pressure. The yield of product is 401g, and it has following property：
Acid number, mg KOH/g： 0.26
In 40 DEG C of viscosity： 32.97
In 100 DEG C of viscosity： 6.20
Viscosity index (VI)： 162
Pour point (DEG C)： -33
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of long-chain ester methyl ester.
1H NMR(CDCl3, ppm)：0.9 [m, 2x-CH3], 1.2-1.6 [m, 22x-CH2-], 2.0 [m, 2x-CH 2 - CH= CH-], 2.1-2.4 [m, 2x-CO-CH2-], 3.5-3.7 [m ,-CH- OH ,-O-CH3], 4.8 [m ,-O-CH-], 5.2-5.6 [m, 2x-CH=CH-CH2-]
Embodiment 3
The preparation of the acetic acid esters of long-chain ester methyl ester：By using the mixture by acetic anhydride (110ml) and pyridine (330ml) The acetylizing agent of composition, by long-chain ester methyl ester acetylation.This acetylizing agent is added in long-chain ester methyl ester (220g) and returns Stream, until acetylization reaction completes.Subsequently reactant mixture is cooled to room temperature, with ether extraction and dilute with q.s HCl treatment is to neutralize pyridine.Ether layer is washed with water makes it not have acid, and passes through sodium sulphate.Remove second under reduced pressure Ether.The acetylate being dried to obtain 197g under vacuum, it has following property：
Acid number, mg KOH/g： 0.49
In 40 DEG C of viscosity： 17.38
In 100 DEG C of viscosity： 4.22
Viscosity index (VI)： 164
Pour point (DEG C)： -33
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of the acetic acid esters of long-chain ester methyl ester.
1H NMR(CDCl3, ppm)：0.9 [m, 2x-CH3], 1.2-1.4 [m, 22x-CH2-], 1.9-2.0 [m, 2x-CH 2 -CH =CH ,-CO-CH3] 2.2 [m, 2x-CO-CH2-], 3.6 [s-O-CH3], 4.8 [m, 2x-O-CH-], 5.2-5.4 [m, 2x-CH= CH-CH2-]
Embodiment 4
The preparation of long-chain ester isopropyl ester：By Castor Oil Fatty Acid long-chain ester (571g) and the isopropanol containing 2% sulfuric acid (118ml) flow back together.Process by thin-layer chromatography monitoring esterification.After completion of the reaction, content is cooled down, use ethyl acetate Extract and wash with water.Make organic layer pass through sodium sulphate, and distill excessive alcohol and ethyl acetate under reduced pressure.Product Yield is 594g, and it has following property：
Acid number, mg KOH/g： 0.03
In 40 DEG C of viscosity： 39.90
In 100 DEG C of viscosity： 7.28
Viscosity index (VI)： 149
Pour point (DEG C)： -27
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of long-chain ester isopropyl ester.
1H NMR(CDCl3, ppm)：0.9 [m, 4x-CH3], 1.2-1.6 [m, 22x-CH2-], 2.0 [m, 2x-CH 2 - CH= CH-], 2.2-2.4 [m, 2x-CO-CH2-], 3.6 [m ,-CH- OH], 4.8-5.0 [m, 2x-O-CH-], 5.3-5.5 [m, 2x CH =CH-CH2-]
Embodiment 5
The preparation of the acetic acid esters of long-chain ester isopropyl ester：By using by acetic anhydride (110ml) and pyridine (330ml) with 1: The acetylizing agent of the mixture composition of 3v/v ratio, by long-chain ester isopropyl ester acetylation.This acetylizing agent is added to long-chain ester different In propyl ester (220g) and flow back, until acetylization reaction completes.Subsequently reactant mixture is cooled to room temperature, is extracted with ether Take, and processed to neutralize pyridine with the watery hydrochloric acid of q.s.Ether layer is washed with water makes it not have acid, and passes through sulfuric acid Sodium.Remove ether under reduced pressure.The acetylate being dried to obtain 214g under vacuum, it has following property：
Acid number, mg KOH/g： 0.08
In 40 DEG C of viscosity： 31.27
In 100 DEG C of viscosity： 6.73
Viscosity index (VI)： 181
Pour point (DEG C)： -30
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of the acetic acid esters of long-chain ester isopropyl ester.
1H NMR(CDCl3, ppm)：0.9 [m, 4x-CH3], 1.2-1.6 [m, 22x-CH2-], 2.0 [m, 2x-CH 2 - CH= CH-, O-CO-CH3] 2.2-2.5 [m, 2x-CO-CH2-], 4.8-5.0 [m, 2x-O-CH-], 5.3-5.5 [m, 2x-CH=CH- CH2-]
Embodiment 6
The preparation of long-chain ester butyl ester：By Castor Oil Fatty Acid long-chain ester (62.5g) and the butanol containing 1% sulfuric acid (100ml) flow back together.After completion of the reaction, content is cooled down, be extracted with ethyl acetate and wash with water.Make organic layer By sodium sulphate, and distill excessive alcohol and ethyl acetate under reduced pressure.The yield of product is 64.3g, and it has following property Matter：
Acid number, mg KOH/g： 0.24
In 40 DEG C of viscosity： 70.39
In 100 DEG C of viscosity： 12.38
Viscosity index (VI)： 176
Pour point (DEG C)： -27
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of long-chain ester butyl ester.
1H NMR(CDCl3, ppm)：0.9 [m, 3x-CH3], 1.2-1.6 [m, 24x-CH2-], 2.0 [m, 2x-CH 2 - CH= CH-], 2.2-2.3 [m, 2x-CO-CH2-], 3.5 [m ,-CH- OH], 4.0 [t ,-O-CH2-], 4.8 [m, O-CH-], 5.3-5.4 [m, 2x-CH=CH-CH2-]
Embodiment 7
The preparation of the acetic acid esters of long-chain ester butyl ester：By using by acetic anhydride (100ml) and pyridine (300ml) with 1: 3v/v The acetylizing agent of the mixture composition of ratio, by long-chain ester butyl ester acetylation.This acetylizing agent is added to long-chain ester butyl ester (220g) in and flow back, until acetylization reaction completes.Subsequently reactant mixture is cooled to room temperature, is extracted with ether, and And processed with the watery hydrochloric acid of q.s to neutralize pyridine.Ether layer is washed with water makes it not have acid, and passes through sodium sulphate.? Decompression is lower to remove ether.The acetylate being dried to obtain 204g under vacuum, it has following property：
Acid number, mg KOH/g： 0.1
In 40 DEG C of viscosity： 25.4
In 100 DEG C of viscosity： 6.30
Viscosity index (VI)： 216
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of the acetic acid esters of long-chain ester butyl ester.
1H NMR(CDCl3, ppm)：0.9 [m, 3x-CH3], 1.2-1.6 [m, 24x-CH2], 2.0 [m, 2x-CH 2- CH= CH-, O-CO-CH3], 2.2-2.3 [m, 2x-CO-CH2-], 2.7 [m ,-CH- OH], 4.0 [t ,-O-CH2-], 4.0 [m, 2x-O- CH-], 5.3-5.4 [m, 2x-CH=CH-CH2-]
Embodiment 8
The preparation of the just own ester of long-chain ester：By Castor Oil Fatty Acid long-chain ester (66g) with contain 0.1%SnCl2N-hexyl alcohol (660ml) flow back together.After completion of the reaction, content is cooled down, be extracted with ethyl acetate and wash with water.Make organic layer By sodium sulphate, and distill excessive alcohol and ethyl acetate under reduced pressure.The yield of product is 69.2g, and it has following property Matter：
Acid number, mg KOH/g： 0.074
In 40 DEG C of viscosity： 56.3
In 100 DEG C of viscosity： 10.13
Viscosity index (VI)： 169
Pour point (DEG C)： -24
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of the just own ester of long-chain ester.
1H NMR(CDCl3, ppm)：0.9 [m, 3x-CH3], 1.2-1.6 [m, 26x-CH2], 2.0 [m, 2x-CH 2 - CH= CH-], 2.2-2.4 [m, 2x-CO-CH2-], 3.5 [m, CH- OH], 4.0 [t, O-CH2-], 4.8 [m ,-O-CH-], 5.2-5.5 [m, 2x-CH=CH-CH2-]
Embodiment 9
The preparation of long-chain ester 2- Octyl Nitrite：By Castor Oil Fatty Acid long-chain ester (700g) with contain 0.1%SnCl22- Ethyl hexanol (374ml) flows back together.After completion of the reaction, content is cooled down, be extracted with ethyl acetate and wash with water. Make organic layer pass through sodium sulphate, and distill excessive alcohol and ethyl acetate under reduced pressure.The yield of product is 808g, and it has Following property：
Acid number, mg KOH/g： 0.49
In 40 DEG C of viscosity： 63.79
In 100 DEG C of viscosity： 10.09
Viscosity index (VI)： 144
Pour point (DEG C)： -36
Flash-point (DEG C)： 252
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of long-chain ester 2- Octyl Nitrite.
1H NMR(CDCl3, ppm)：0.9 [m, 4x-CH3], 1.2-1.6 [m, 26x-CH2], 2.0 [m, 2x-CH 2 - CH= CH-], 2.2-2.3 [m, 2x-CO-CH2-], 3.5 [m ,-CH-OH], 4.0 [d, O-CH2-], 4.8 [m ,-O-CH-], 5.2-5.5 [m, 2x CH=CH-CH2-]
Embodiment 10
The preparation of the acetic acid esters of long-chain ester 2- Octyl Nitrite：By using by acetic anhydride (153ml) and pyridine (459ml) The acetylizing agent of mixture composition, by the Octyl Nitrite acetylation of long-chain ester 2-.This acetylizing agent is added to long-chain ester 2- ethyl In own ester (373g) and flow back, until acetylization reaction completes.Subsequently reactant mixture is cooled to room temperature, is extracted with ether Take, and processed to neutralize pyridine with the watery hydrochloric acid of q.s.Ether layer is washed with water makes it not have acid, and passes through sulfuric acid Sodium.Remove ether under reduced pressure.The acetylate being dried to obtain 348g under vacuum, it has following property：
Acid number, mg KOH/g： 0.20
In 40 DEG C of viscosity： 42.7
In 100 DEG C of viscosity： 8.35
Viscosity index (VI)： 175
Pour point (DEG C)： -39
Flash-point (DEG C)： 262
Cu bar corrosion number： 1a
Raw product is carried out1H NMR spectra is studied, to determine the formation of the acetic acid esters of long-chain ester 2- Octyl Nitrite.
1H NMR(CDCl3, ppm)：0.9 [m, 4x-CH3], 1.2-1.6 [m, 26x-CH2-], 1.9-2.0 [m, 2x-CH 2 -CH =CH-, O-CO-CH3], 2.2-2.3 [m, 2x-CO-CH2-], 3.9-4.0 [d, O-CH2-], 4.8 [m ,-O-CH-], 5.2-5.4 [m, 2x-CH=CH-CH2-]
Advantages of the present invention：
1. the advantage of long-chain ester derivant of the present invention is that their high viscosity index (VI)s (VI) and more than ISO VG32's is viscous Degree grade, they are preferably.
2. these long-chain ester derivants may not be needed for improving thickener necessary to viscosity, VI, and polymer The presence of base thickener or modifying agent may cause shear stable sex chromosome mosaicism in the lubricating oil prepared.
3. cryogenic property is important for lubricating oil pumping, filterability, mobility and cold start and startup.Pour point It is the most common index of low temperature behavior.Oil base stock derived from vegetable oil is not generally in the case of adding pour-point depressant There is high pour point.The long-chain ester derivant of present invention tool compared with more high-viscosity trioleate, vegetable oil or polyol ester There is excellent cryogenic property.
4. generally it is contemplated that the long-chain ester derivant of the present invention have in terms of their oxidation stability and cryogenic property excellent Advantage in other vegetable oil based lubricating oils.

Claims (4)

1. a kind of method of the long-chain ester for preparing formula 1,
Wherein the mean value of n makes the acid number of long-chain ester be equal to 95 equal to 1, and it corresponds to average two points in described long-chain ester The castor oil acid of son,
R1It is the group selected from methyl, isopropyl, hexyl and 2- ethylhexyl composition；R2Part is CH3CO,
Wherein said method includes：
I () saponification castor oil obtains castor oil acid, by described castor oil acid between 175 to 190 DEG C in the range of temperature, lazy Property atmosphere under heat time in the range of between 3 to 5hr, obtain the long-chain ester compounds of formula 1, the wherein mean value of n is 1, And R1And R2It is H,
(ii) selected from sulfuric acid or SnCl2In catalyst in the presence of, in reflux temperature or at 140 to 160 DEG C between in the range of Temperature, makes the long-chain ester compounds 1 obtaining in step (i) and methyl alcohol, isopropanol, n-hexyl alcohol or 2-Ethylhexyl Alcohol react 3 Time in the range of to 8hr, to obtain corresponding long-chain ester ester,
(iii) the long-chain ester ester obtaining in step (ii) is made to react with acetic anhydride and pyridine, to obtain the long-chain ester ester of formula 1 Acetyl compounds, wherein R1Part is selected from methyl, isopropyl, the group of hexyl and 2- ethylhexyl composition, and R2Part It is CH3CO.
2. the method for claim 1, the acid number of wherein said compound is 0.5mgKOH/g.
3. the method for claim 1, the compound of its Chinese style 1 is suitable for former state or is acted as with blend composition or additive one Oil base stock for functional fluid.
4. a kind of long-chain ester compounds of the formula 1 being obtained by the method described in claim 1,
Wherein the mean value of n makes the acid number of long-chain ester be equal to 95 equal to 1, and it corresponds to average two points in described long-chain ester The castor oil acid of son,
R1It is the group selected from methyl, isopropyl, hexyl and 2- ethylhexyl composition；R2Part is CH3CO.
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